Electrocatalysts are of great importance for water splitting to produce hydrogen. Here, NiO and CrO3 double surface-decorate Ni (Ni@NiO@CrO3) nanofibers were prepared by electrospinning as highly effective and stable electrocatalysts for hydrogen evolution reaction. It shows high electrocatalytic activity (100 mA cm(-2) at a low overpotential versus RHE at 228 mV) and superior stability (after 120 h without decay). The excellent electrocatalytic activity of Ni@NiO@CrO3 nanofibers is account for the well distribution of CrO3 nanoparticles and the good conductivity of Ni nanowires. As CrO3 nanoparticles are partly embedded in the nanofibers, they are difficult to peel off from the Ni@NiO nanofibers, enabling a good stability of the hybrid materials. (C) 2016 Elsevier B.V. All rights reserved.